CN105121476A - Oil extended functionalized styrene-butadiene copolymer - Google Patents
Oil extended functionalized styrene-butadiene copolymer Download PDFInfo
- Publication number
- CN105121476A CN105121476A CN201480022344.0A CN201480022344A CN105121476A CN 105121476 A CN105121476 A CN 105121476A CN 201480022344 A CN201480022344 A CN 201480022344A CN 105121476 A CN105121476 A CN 105121476A
- Authority
- CN
- China
- Prior art keywords
- oil
- functionalized
- styrene
- butadiene copolymer
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 54
- 239000003921 oil Substances 0.000 claims abstract description 190
- 235000019198 oils Nutrition 0.000 claims abstract description 186
- 239000000178 monomer Substances 0.000 claims abstract description 62
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 32
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 7
- 239000008158 vegetable oil Substances 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims description 123
- 239000005060 rubber Substances 0.000 claims description 123
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 103
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 90
- 239000003549 soybean oil Substances 0.000 claims description 56
- 235000012424 soybean oil Nutrition 0.000 claims description 56
- 239000000377 silicon dioxide Substances 0.000 claims description 54
- 229960001866 silicon dioxide Drugs 0.000 claims description 52
- 235000012239 silicon dioxide Nutrition 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 38
- 239000006229 carbon black Substances 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 29
- 229920000126 latex Polymers 0.000 claims description 29
- 239000004816 latex Substances 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 27
- -1 methyl glycidyl Chemical group 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 25
- 210000000582 semen Anatomy 0.000 claims description 24
- 230000008859 change Effects 0.000 claims description 23
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 23
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 14
- 235000011007 phosphoric acid Nutrition 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 150000002924 oxiranes Chemical group 0.000 claims description 13
- 239000007853 buffer solution Substances 0.000 claims description 12
- 235000013311 vegetables Nutrition 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 11
- 239000007836 KH2PO4 Substances 0.000 claims description 10
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 10
- 238000005227 gel permeation chromatography Methods 0.000 claims description 10
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 10
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 10
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- 229910021538 borax Inorganic materials 0.000 claims description 9
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000001488 sodium phosphate Substances 0.000 claims description 9
- 239000004328 sodium tetraborate Substances 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- VUZHZDBMVSHDRE-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OCCCOC(=O)C=C VUZHZDBMVSHDRE-UHFFFAOYSA-N 0.000 claims description 8
- 238000006735 epoxidation reaction Methods 0.000 claims description 8
- 239000000944 linseed oil Substances 0.000 claims description 8
- 235000021388 linseed oil Nutrition 0.000 claims description 8
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 8
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 8
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 241000221089 Jatropha Species 0.000 claims description 6
- 240000007594 Oryza sativa Species 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 235000019483 Peanut oil Nutrition 0.000 claims description 6
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 241000269319 Squalius cephalus Species 0.000 claims description 6
- 235000019486 Sunflower oil Nutrition 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 239000000828 canola oil Substances 0.000 claims description 6
- 235000019519 canola oil Nutrition 0.000 claims description 6
- 235000009508 confectionery Nutrition 0.000 claims description 6
- 239000000312 peanut oil Substances 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 239000008159 sesame oil Substances 0.000 claims description 6
- 235000011803 sesame oil Nutrition 0.000 claims description 6
- 239000002600 sunflower oil Substances 0.000 claims description 6
- 239000013638 trimer Substances 0.000 claims description 6
- UNIYDALVXFPINL-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propylsilicon Chemical compound CC(=C)C(=O)OCCC[Si] UNIYDALVXFPINL-UHFFFAOYSA-N 0.000 claims description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 5
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 229940093916 potassium phosphate Drugs 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 125000005457 triglyceride group Chemical group 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 229940061607 dibasic sodium phosphate Drugs 0.000 claims description 3
- PEMGHGXQUNLSDF-UHFFFAOYSA-L dipotassium;2-carboxybenzoate Chemical compound [K+].[K+].OC(=O)C1=CC=CC=C1C([O-])=O.OC(=O)C1=CC=CC=C1C([O-])=O PEMGHGXQUNLSDF-UHFFFAOYSA-L 0.000 claims description 3
- NGATWIKLQRJVRN-UHFFFAOYSA-N phthalic acid;sodium Chemical compound [Na].[Na].OC(=O)C1=CC=CC=C1C(O)=O NGATWIKLQRJVRN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000004606 Fillers/Extenders Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 68
- 239000000126 substance Substances 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 18
- 238000005096 rolling process Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 15
- 208000034189 Sclerosis Diseases 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 230000006872 improvement Effects 0.000 description 10
- 230000003993 interaction Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000000753 cycloalkyl group Chemical group 0.000 description 9
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 244000068988 Glycine max Species 0.000 description 4
- 235000010469 Glycine max Nutrition 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 239000004045 soybean oil emulsion Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 3
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- 238000012545 processing Methods 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
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- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 2
- LIZVXGBYTGTTTI-UHFFFAOYSA-N 2-[(4-methylphenyl)sulfonylamino]-2-phenylacetic acid Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C(O)=O)C1=CC=CC=C1 LIZVXGBYTGTTTI-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical compound BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-UHFFFAOYSA-N 0.000 description 1
- JZYAVTAENNQGJB-UHFFFAOYSA-N 3-tripropoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCOC(=O)C(C)=C JZYAVTAENNQGJB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- IPCWTALQCRIHLP-UHFFFAOYSA-N C(C=C)(=O)OCCCO.CC=CC(=O)O Chemical compound C(C=C)(=O)OCCCO.CC=CC(=O)O IPCWTALQCRIHLP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 239000005065 High vinyl polybutadiene Substances 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- UIJDAGBZCJCLNO-UHFFFAOYSA-N [dimethoxy(methyl)silyl]methyl prop-2-enoate Chemical compound CO[Si](C)(OC)COC(=O)C=C UIJDAGBZCJCLNO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- FMMOOAYVCKXGMF-MURFETPASA-N ethyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC FMMOOAYVCKXGMF-MURFETPASA-N 0.000 description 1
- 229940031016 ethyl linoleate Drugs 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ODHYIQOBTIWVRZ-UHFFFAOYSA-N n-propan-2-ylhydroxylamine Chemical compound CC(C)NO ODHYIQOBTIWVRZ-UHFFFAOYSA-N 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010091 synthetic rubber production Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- GQLBMRKEAODAKR-UHFFFAOYSA-L zinc;selenate Chemical compound [Zn+2].[O-][Se]([O-])(=O)=O GQLBMRKEAODAKR-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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Abstract
The present invention refers to an oil extended functionalized styrene-butadiene copolymer wherein the functionalized styrene-butadiene copolymer comprises 1 to 50 wt.%, based on 100 wt.% of the copolymer, of repeating units based on styrene, 42 to 80 wt.%, based on 100 wt.% of the copolymer, of repeating units based on butadiene, and 5 to 43 wt.%, based on 100 wt.% of the copolymer, of units based on at least one functional monomer and wherein at least one extender oil is based on vegetable oils, preferably epoxidized vegetable oil.
Description
Technical field
The present invention relates to a kind of oil-filled functionalized styrene-butadiene copolymer, its method and uses thereof.
Background technology
Carried out much research, these researchs are the character by functionalized reagent's modified dienopolymer and multipolymer.
The sense ESBR that one has glycidyl methacrylate (GMA) is described in U.S. Patent Application No. 2011/0098404A1.According to ladies and gentlemen contriver, " styrene-butadiene copolymer obtained by letex polymerization presents the consistency with the difference of silicon-dioxide ".In this patent application, ladies and gentlemen contriver reports the functionalized styrene-butadienecopolymer by letex polymerization exploitation in the following manner with the silicon-dioxide consistency of improvement: use a kind of epoxy acrylate monomer polymerization styrene-butadiene copolymer and the sulfuric acid (H of then use 20%
2sO
4) or the aqueous solution of potassium hydroxide (KOH) carry out the open loop of epoxy group(ing).This sense ESBR is used in compound preparation together with silicon-dioxide, it is said that it has superior tensile properties, wear resistance and dampness (wetstopping) (the tan δ at 0 DEG C).A kind of functionalized styrene-butadienecopolymer with monomer of this patent application hereby claims, these monomers have functional group as amine, hydroxyl, alkoxyl group, sulphonate, carboxylicesters, phosphonic acid ester, halogen, mercaptan and trinitride; For silicon dioxide composite material and a kind of method for the preparation of described functionalized styrene-butadienecopolymer of tire, flexible pipe or belt, the method comprises the open loop carrying out epoxy.
The rubber of hardening product of wear resistance that there is low-rolling-resistance, good wet earth-grasping force (wetskid) and improve of a kind of production for doughnut tyre surface is described in U.S. Patent number 6,699,935B2.Ladies and gentlemen contriver uses polymerisable unsaturated group, as Vinylstyrene, carboxyl, hydroxyl and/or epoxy group(ing).In this patent, report is can reduce rolling resistance by the hysteresis loss (low Thermal release) reducing rigidified rubber.Inorganic filler is used to show low-rolling-resistance and excellent riding stability (wet earth-grasping force) as the tire tread of silicon-dioxide.On the other hand, they show the tensile strength and wear resistance of going on business.Reason is considered to the interaction of the difference of polymer-silica compared with carbon black.In order to overcome this problem, proposed obtain one have possibility can with the polymkeric substance of inorganic filler (silicon-dioxide) interactional functional group.But, because these groups promote and the strong interaction of polymkeric substance, it create weighting agent dispersion, the problem of the workability of Thermal release and difference in the course of processing.The challenge of researchist is that find can the functional monomer being bonded to the appropriate amount in this polymkeric substance of binding characteristic and workability.U.S. Patent number 6,699,935B2 requires a kind of rubber combination, and this rubber combination has polymerisable monomer, and this polymerisable monomer has functional group, and this functional group comprises carboxyl, amino, hydroxyl, epoxy group(ing) and alkoxysilyl.The example of carboxylic group: (methyl) vinylformic acid, toxilic acid, methylene-succinic acid and analogue.Amino example: (methyl) acrylate methyl esters, (methyl) vinylformic acid diethylamino methyl esters, N, N-diethyl-p-aminostyryl, 2-vinyl pyridine and analogue.The example of hydroxyl: (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, p-hydroxy styrenes and analogue.The example of epoxide group: (methyl) allyl glycidyl ether (allyglycidylether), (methyl) glycidyl acrylate and (methyl) vinylformic acid 3,4-oxygen cyclohexyl.The example of alkoxysilane groups: (methyl) acryloyloxymethyl Trimethoxy silane, (methyl) acryloyloxymethyl dimethoxysilane, γ-methacryloxypropyl tripropoxy silane and analogue.In this invention it is mentioned that the combination that two or more have the functional monomer of carboxyl, hydroxyl or epoxy group(ing) may be had.For example, it is possible that have the combination of carboxylic monomer and carboxylic monomer.U.S. Patent number 6,699,935 also require that a kind of tire composition with the functional polymer mentioned.
U.S. Patent number 4,574, the 140 a kind of methods disclosing synthetic elastomer multipolymer for obtaining " wet tenacity " with improvement, should " wet tenacity " be defined as in the invention " polymkeric substance common in natural rubber or elastomeric characteristic; it contributes to suitable construction conditions, recorded by stress-strain measurement usually ".Utilize conventional practice and program (as temperature, pressure and time) by the letex polymerization of radical initiator by free radical for obtaining the method for this base polymer.Letex polymerization is being carried out, although author states that it should not be limited under the pH of 10 to 11.These can be had hang hydroxyl from above polymkeric substance in banbury with other copolymer blended, these other multipolymers are as natural rubber, cis and trans polybutadiene, cis and using trans-polyisoprene, polypropylene, divinyl and cinnamic multipolymer, the multipolymer of alpha-methyl styrene and divinyl, high-cis-1,4-polyisoprene and high-cis-1，4-polybutadiene.This is blended can be undertaken by the form of latex and can with elastomerics as the multipolymer of polyhutadiene, vinylbenzene and divinyl and the latex of butyronitrile latex mix.This trimer can be partial cross-linked by adding linking agent (as vulcabond).For making the example of the monomer of this functionalization of polymers be: Rocryl 410, hydroxyethyl methylacrylate, Hydroxyethyl acrylate and Propylene glycol monoacrylate.The example 3 of this invention shows the trimer of following item: styrene butadiene-HEMA (hydroxyethyl methylacrylate) and styrene butadiene and glycidyl methacrylate (GMA).These latexes are carried out stripping, condensation and use formula in carbon black mixing.According to ladies and gentlemen contriver, HEMA trimer compound shows elasticity more better than GMA trimer compound.A kind of method of synthetic elastomer multipolymer of wet tenacity for the formation of having improvement of this patent requirements, the method comprises makes the synthetic elastomer of at least one type form monomer and hydroxyl reaction, wherein said hydroxyl monomer is selected from lower group, and this group is made up of the following: hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate and Propylene glycol monoacrylate.
U.S. Patent number 6,653,404B2 describe a kind of for obtain have functional monomer (as (methyl) vinylformic acid diethylamino methyl esters, (methyl) Propylene glycol monoacrylate, neighbour, p-hydroxy styrenes, (methyl) glycidyl acrylate, alkoxysilyl groups (methyl) acryloyloxymethyl Trimethoxy silane and analogue) the method for rubber.According to this invention, rubber combination presents workability that is gratifying and silicon-dioxide.The rubber combination allegedly with silicon-dioxide and carbon black has excellent tensile strength and wear resistance.
U.S. Patent number 7,108,033B2 discloses the invention for obtaining polymkeric substance, and these polymer exhibits go out low consistency that is delayed and good and weighting agent (as carbon black and silicon-dioxide).Functional monomer is derived from one or more conjugate diene monomers, and these conjugate diene monomers have leavings group as halogen (chlorine, bromine and iodine).According to ladies and gentlemen contriver, this polymerization system can be carried out by mass polymerization, vapor phase polymerization, solution polymerization, suspension and letex polymerization, but letex polymerization is commercial preferred one.The example of these monomers is: 4-vinyl benzyl muriate, 4-vinyl benzyl bromide, 4-vinyl benzyl thiocyanic ester.Use the carbon black in formula and silicon-dioxide mixing functional polymer.The compound that dynamic test shows from the functional polymer with 4-vinyl benzyl muriate shows delayed minimizing, and this is the instruction improved in the interaction of polymer-filler agent (main and silicon-dioxide).A kind of tire of this patent requirements, this tire is made up of with the composition like rubber with the functional monomer mentioned the carcass of the annular shape generally with outer longitudinal tyre surface (circumferentialtread).
U.S. Patent number 6,455,655B1, U.S. Patent number 6,512,053B1 and U.S. Patent number 6,716,925B2 discloses a kind of emulsion styrene-butadiene rubber (ESBR), and when using in for the preparation of tire tread, this rubber has those the characteristic (as rolling resistance and treadwear) that is similar to solution S BR but has the tractive characteristic of improvement.The feature of this rubber is in conjunction with hydroxy alkyl acrylate monomer in polymer chain, methacrylate hydroxypropyl acrylate or rather.In U.S. Patent number 6,455,655B1 and U.S. Patent number 6,512,053B1, produce respectively and there is low and latex that is high molecular.In U.S. Patent number 6,455,655B1, methacrylate hydroxypropyl acrylate monomer preferably combined in the course of the polymerization process for obtain high molecular rubber and its horizontal extent from about 3 weight percents to about 5 weight percents.Polymerization temperatures range is from 7 DEG C to 13 DEG C.High molecular will be had and there is low-molecular-weight latex and carry out blended and condense with salt solution and dilute sulphuric acid or Tai-Ace S 150.Wash and dry chip.In order to obtain desired characteristic, the emulsion SBR this can invented and other polymer blendings and co-curing.The example of this base polymer comprises natural rubber, high-cis-1,4-polyhutadiene, high vinyl polybutadiene, medium vinyl polybutadiene, high trans-1,4-polyhutadiene, solution styrene-butadiene, styrene-isoprene-divinyl, styrene-isoprene, isoprene-butadiene and 3,4-polyisoprene.U.S. Patent number 6,455,655B1 requires a kind of styrene butadiene rubbers composition and a kind of tire, in this styrene butadiene rubbers composition this hydroxy alkyl acrylate, especially methacrylate hydroxypropyl acrylate with scope from the horizontal integration of about 3% to about 5% this polymkeric substance, this tire has the tyre surface be made up of the styrene butadiene rubbers composition of specifying in this invention, and wherein weighting agent is selected from the group be made up of carbon black and silicon-dioxide.
Under prior art level it is well known that when producing with high molecular ESBR polymer exhibits go out their better properties with regard to rolling resistance, tear strength and wear resistance.But those high-molecular weight polymers are difficult to be generally used for processing in the blending equipment in compounding rubber industry.
In order to overcome this technical problem, practice general in synthetic rubber production plant is bonded to by extending oil (extensionoil) in high-molecular weight polymer to improve their workabilitys in compounding rubber factory.
The horizontal file of prior art described above and usual technical literature do not comment on the effect of extending oil in the characteristic or workability of polar-modified ESBR.They mainly concentrate on the polar functional reagent in introducing polymer chain, and do not note the chemical property having extending oil to be used.
Extending oil for ESBR is the key ingredient of consistency, workability and the characteristic being used to indicate them.For this reason, it is highly important that extending oil is chemically compatible with the polymer backbone for mixing and weighting agent.
The extending oil used in ESBR produces at present is from fossil sources and based on the nonpolar moiety of petroleum hydrocarbon, these petroleum hydrocarbons have a certain composition of aromatics, naphthenic compound and paraffinic compound.
In this order, aromatics is more compatible to ESBR polymer chain than naphthenic compound and paraffinic compound.Identical about carbon black consistency order.
But oil distillate to be more rich in paraffinic compound and to it is highly important that this compounds that the level controlling aromatic carbon and cycloalkanes carbon is minimally measured in the extending oil for ESBR modification for this reason.
In addition, height perfume oil is forbidden by rubber industry, recently due to the PAH (polyaromatic) of its high-content.They are replaced by TRAE (the residual aromatic series extract processed), TDAE (the overhead product aromatic series extract processed), MES (gentle Extraction solvent compound), HN (high cyclic hydrocarbon) and other low PAH oil.But those oil still there is the PAH compound of a tittle and they are all derived from the non-renewable source of the various process distilled from raw petroleum.
Summary of the invention
The present invention discloses a kind of oil-filled functionalized styrene-butadiene copolymer, wherein this functionalized styrene-butadiene copolymer comprise the styrene-based of 15 to the 50wt.% of this multipolymer based on 100wt.% repeating unit, based on the repeating unit based on divinyl of 42 to the 80wt.% of this multipolymer of 100wt.% and 5 to the 43wt.% of this multipolymer based on 100wt.% the unit based at least one functional monomer and wherein at least one extending oil be based on vegetables oil.
Preferably, this functional monomer and this styrene monomer and butadiene monomers are to form this functionalized multipolymer, and therefore this multipolymer represents a kind of functionalized trimer.
Preferably, this oil-filled functionalized styrene-butadiene copolymer comprises 0.3 to 10wt.%, preferably 0.5 to the 5.0wt.% of this multipolymer based on 100wt.% and the unit based on this functional monomer of more preferably 0.7 to 3.5wt.%.
This oil-filled functionalized styrene-butadiene copolymer preferably has the mooney viscosity (ML1+4 at 100 DEG C) of 35 to 65, preferably 40 to 60, and passes through the molecular-weight average (Mw) of 100.000 to 2.200.000g/mol, preferably 200.000 to 900.000g/mol that GPC (gel permeation chromatography) determines.
Preferably, this functional monomer is grafted on this multipolymer.
Preferably, this functional monomer is selected from lower group, this group is made up of the following: acrylate base monomer preferable methyl glycidyl acrylate, glycidyl acrylate, methacrylate hydroxypropyl acrylate, hydroxyethyl methylacrylate, vinyl cyanide, methacryloxypropyl trimethoxy silane, methacryloxypropyl three isopropoxy silane, or methacryloxypropyl silane.
Preferably, this extending oil is selected from lower group, and this group is made up of the following: soybean oil, Oleum Gossypii semen, Semen Ricini oil, plam oil, linseed oil, Oleum Cocois, sunflower oil, pine-tree oil, Semen Maydis oil, sweet oil, peanut oil, rapeseed oil, Canola Oil, sesame oil, Rice pollard oil, Jatropha oil with and composition thereof.
This extending oil of preferably transesterify, more preferably epoxidation.
In a preferred embodiment, this extending oil is used with 25 to 42phr, the preferably amount of 37.5phr.
The present invention discloses a kind of method in ESBR polymkeric substance for polar comonomers being introduced into containing epoxide group, this epoxide group keeps stable in the course of the polymerization process and does not have open loop and therefore illustrate the workability with the excellence of silicon dioxide compound.
Preferably, the method for the production of this oil-filled functionalized styrene-butadiene copolymer comprises:
(1a) use a kind of buffer system and control pH Emulsion polymerized styrene in the scope of 8.5 to 9.5 of latex, divinyl and functional monomer, wherein this buffer system is selected from lower group, this group is made up of the following: phthalic acid disodium hydrogen/sodium dihydrogen orthophosphate, acetic acid/sodium acetate, boric acid/sodium tetraborate, dibasic sodium phosphate/sodium hydroxide, monosodium phosphate/phosphoric acid, KH2PO4/sodium hydroxide, Di-Sodium Phosphate/phosphoric acid, monosodium phosphate/sodium hydroxide, boric acid/sodium hydroxide, hydrogen phthalate dipotassium/KH2PO4, KH2PO4/sodium hydroxide, sodium tetraborate/hydrochloric acid, sodium carbonate/bicarbonate, Di-Sodium Phosphate/phosphoric acid, potassiumphosphate/potassium hydroxide, sodium tetraborate/sodium hydroxide, sodium bicarbonate/sodium hydroxide, ortho-phosphoric acid hydrogen sodium/sodium hydroxide, Repone K/sodium hydroxide, or
(1b) by a kind of styrene-butadiene copolymer of being obtained by Emulsion polymerized styrene and divinyl and functional monomer's grafting, and
(2) this analog copolymer that will be obtained by (1a) or (1b) and at least one blended based on the extending oil of vegetables oil.
Preferably, functional monomer for described method is selected from lower group, this group is made up of the following: acrylate base monomer is as glycidyl methacrylate, glycidyl acrylate and analogue, methacrylate hydroxypropyl acrylate, hydroxyethyl methylacrylate and analogue, vinyl cyanide, methacryloxypropyl trimethoxy silane, methacryloxypropyl three isopropoxy silane, methacryloxypropyl silane and analogue.
Preferably, extending oil for described method is selected from lower group, and this group is made up of the following: soybean oil, Oleum Gossypii semen, Semen Ricini oil, plam oil, linseed oil, Oleum Cocois, sunflower oil, pine-tree oil, Semen Maydis oil, sweet oil, peanut oil, rapeseed oil, Canola Oil, sesame oil, Rice pollard oil, Jatropha oil or its mixture.
In a preferred embodiment, transesterify is used for the extending oil of described method makes it have mixture based on 100wt.% from the fatty-acid ethyl ester of 5 to 60wt.%, the mixture of the triglyceride from 40 to 80wt.% and the triglyceride level from 0.01 to 99.9wt.%, preferably produce by the fatty-acid ethyl ester from 35% to 48% change, the composition of the triglyceride from 50% to 75% change and the triglyceride level composition from 0.01% to 50% change, and more preferably produce by the fatty-acid ethyl ester from 40% to 44% change, the composition of the triglyceride from 56% to 60% change and the triglyceride level composition from 0.01% to 4% change.
In a further advantageous embodiment, the extending oil of this transesterify of epoxidation make it have 2.5% to 4.5% and preferably 3.3% to 3.5% epoxidation level.
The invention also discloses the purposes of epoxidised renewable extending oil, these extending oils are compatible with epoxidised ESBR described above and the characteristic (as rolling resistance, wet grip, wear resistance and tear strength) of excellence is given the compound prepared as weighting agent with silicon-dioxide and/or carbon black.
Another invention or a kind of rubber combination, this rubber combination comprises oil-filled functionalized styrene-butadiene copolymer of the present invention and at least one carbon black and/or at least one silicon-dioxide.
Preferably, the present invention also comprises this rubber combination for the production of technology article, the purposes of preferred tire, tyre surface, conveying belt, sole, pipeline, carpet-like coverture, flexible pipe and moulded product.
In this application, term " reproducible " refers to the oil of non-fossil sources, comprise all vegetables oil mentioned in this application, these vegetables oil are selected from soybean oil, Oleum Gossypii semen, Semen Ricini oil, plam oil, linseed oil, Oleum Cocois, sunflower oil, pine-tree oil, Semen Maydis oil, sweet oil, peanut oil, rapeseed oil, Canola Oil, sesame oil, Rice pollard oil, Jatropha oil or its mixture, preferred soybean oil, Oleum Gossypii semen, Semen Ricini oil, plam oil and linseed oil, preferred soybean oil and Oleum Gossypii semen and more preferably soybean oil.
The rubber using the standard ESBR filled by general soybean oil to obtain is used to preparation using silicon-dioxide and/or carbon black as the compound of weighting agent, but the mechanical characteristics of hardening product and wear resistance are non-constants, show oil to ooze out, owing to the low interaction of polymkeric substance-oil.
By polymkeric substance and renewable extending oil functionalized after overcome this technical problem.Therefore, the present invention proposes and obtain functionalized latex (there is the epoxide group along polymeric chain) and then in conjunction with esterification and epoxidised renewable oils, preferred epoxidised soybean oil.
Compared with the standard rubbers of filling by general soybean oil, the rubber compound with silicon-dioxide and/or carbon black using new rubber of the present invention to prepare presents the characteristic of improvement.
This new rubber developed in the present invention does not present oil and oozes out and the rubber hardening product (the suitable consistency due to polymkeric substance and extending oil) excellent and superior characteristic being given acquisition related to this.
Therefore, the present invention relates to a kind of method for being produced oil-filled functionalized styrene-butadiene copolymer by letex polymerization, the method comprises the following steps:
(1a) use a kind of buffer system and control pH Emulsion polymerized styrene, divinyl and functional monomer in the scope of 8.5 to 9.5 of latex pH, so that retaining ring oxygen groups is stable and do not have open loop; And
(2) this analog copolymer that will be obtained by (1a) and at least one based on vegetables oil extending oil, preferably epoxidized vegetable oil is blended.
In a preferred embodiment, the present invention relates to a kind of method for being produced oil-filled functionalized styrene-butadiene copolymer by letex polymerization, the method comprises the following steps:
(1b) by carrying out directly this polymer chain functionalized via with this general ESBR of polymeric chain modification of the functionalized general ESBR of epoxide group; And
(2) this analog copolymer that will be obtained by (1b) and at least one based on vegetables oil extending oil, preferably epoxidized vegetable oil is blended.
A preferred embodiment, the present invention relates to a kind of oil-filled functionalized styrene-butadiene copolymer, wherein this styrene monomer be with this multipolymer based on 100wt.% by weight 15% to 50% (wt.%) amount exist, this divinylic monomer be with this multipolymer based on 100wt.% by weight 42% to 80% amount exist, this extending oil exists with the amount of 25 to 42phr, more preferably 37.5phr.
Preferably oil-filled functionalized styrene-butadiene copolymer presents the mooney viscosity (ML1+4 of 35 to 65, preferably 40 to 60,100 DEG C), and pass through the molecular-weight average (Mw) of 100.000 to 2.200.000g/mol, preferably 200.000 to 900.000g/mol that GPC (gel permeation chromatography) determines.
In a preferred embodiment, the present invention relates to a kind of rubber combination, this rubber combination comprises carbon black and/or silicon-dioxide as weighting agent and oil-filled functionalized styrene butadiene as described above (obtainable preferably by method of the present invention).
In a preferred embodiment, the present invention relates to and comprise carbon black and/or the silicon-dioxide rubber combination as weighting agent and oil-filled functionalized styrene-butadiene copolymer for the manufacture of the purposes of technology article, these technology articles are generally as tire, tyre surface, conveying belt, sole, pipeline, carpet-like coverture, flexible pipe and moulded product.
In a preferred embodiment, the present invention relates to oil-filled functionalized styrene-butadiene copolymer for the manufacture of comprising carbon black and/or the silicon-dioxide purposes as the rubber combination of weighting agent.
In a preferred embodiment, the present invention relates to renewable oils by the purposes of letex polymerization for the production of oil-filled functionalized styrene-butadiene copolymer.
In a preferred embodiment, the present invention relates to by the obtainable oil-filled functionalized styrene-butadiene copolymer of method of the present invention.
Accompanying drawing explanation
Fig. 1: the spectrum of the GMA monomer obtained by Fourier transform infrared (FTIR) technology.
Fig. 2: the spectrum of the standard ESBR of preparation in the example of the present invention 1 obtained by Fourier transform infrared (FTIR) technology.
Fig. 3: the spectrum of the functionalized ESBR of preparation in the example of the present invention 4 obtained by Fourier transform infrared (FTIR) technology.
Fig. 4: the signal thermogram (mass loss and derivative reduced temperature) of the vegetables oil sample after transesterification reaction.
Embodiment
The polymkeric substance with functional group presents the interaction with the improvement of weighting agent (principal silica), and these weighting agents also have functional group's (hydroxyl and siloxane groups).The interact hysteresis loss (low heat emission) of better hardening compound of polymer-filler agent is lower and therefore reduce rolling resistance, this means fuel consumption economy.
It is known that compared to carbon black, silicon-dioxide as reinforcing filler by the mechanical characteristics of improvement, rolling resistance and other be supplied to tire.
Functionalized ESBR of the present invention can be produced by the free-radical emulsion polymerization of the functional monomer using monomer styrene, divinyl and have functional group's (as epoxy group(ing), hydroxyl etc.).Styrene monomer is so that the amount of 20% to 40% is present in this polymeric chain by weight by weight 15% to 50%, preferably.The vinylbenzene amount being less than 15% by weight in this polymeric chain means the loss of characteristic (as mechanical characteristics etc.).Caoutchouc elasticity, wear resistance will be damaged higher than the vinylbenzene amount of 50% and also have workability by weight.Divinylic monomer is so that the amount of 45% to 75% is present in this polymeric chain by weight by weight 42% to 80%, preferably.The divinyl amount being less than 42% by weight in this polymeric chain means the wear resistance etc. of the difference of rigidified rubber.Divinyl amount higher than 80% causes the reduction etc. in mechanical characteristics etc.
Functionalized ESBR of the present invention presents the molecular-weight average (Mw) by 100.000 to the 2.200.000g/mol of GPC (gel permeation chromatography), preferably 200.000 to 900.000g/mol.
Functionalized ESBR of the present invention can use different polymerisable functional monomers to be prepared as the third monomer (usually to use not damage workability in a small amount).Polymerizable functionalities monomer of the present invention must have polar group.That epoxy acrylate monomer is as glycidyl methacrylate, glycidyl acrylate and analogue as the example being applicable to polymerizable functionalities monomer of the present invention, methacrylate hydroxypropyl acrylate, hydroxyethyl methylacrylate and analogue, vinyl cyanide, methacryloxypropyl trimethoxy silane, methacryloxypropyl three isopropoxy silane, vinyltrimethoxy silane, methacryloxypropyl silane and analogue.Epoxy acrylate monomer is preferred and more preferably glycidyl methacrylate (GMA).
This glycidyl methacrylate with relative to total monomer by weight 0.3% to 10% amount, preferably with 0.5% to 5.0% amount and be more preferably present in this polymer chain with the amount of 0.7% to 3.5%.
Glycidyl methacrylate monomer is represented by following chemical structure 1:
Glycidyl methacrylate is combined along polymeric chain randomly in polymerization process, obtains a kind of functionalized ESBR (chemical structure 2) with epoxide group.These polar groups improve at polymkeric substance, weighting agent and also have interaction between epoxidised vegetables oil, avoid and have silicon-dioxide and/or carbon black as oozing out on the hardening compound of weighting agent.
Also possibly by carrying out the directly functionalized of this polymeric chain via with the polymeric chain modification general ESBR latex of the functionalized general ESBR latex of epoxide group.The general latex of epoxidation is well-known method and can uses organic peracid (preferred peroxybenzoic acid and metachloroperbenzoic acid); Superoxide and hydroperoxide (preferred benzoyl peroxide); Peroxyformic acid and peracetic acid (by adding respectively in reaction medium, formic acid and acetic acid and hydrogen peroxide in situ produces) carry out.The emulsion of epoxidised renewable oils of the present invention can be mixed with the epoxidised latex obtained by above technology and condenses, obtain the epoxidezed rubber that a kind of functionalized renewable oils is filled.
Epoxy natural rubber latex is also a kind of well-known method and is usually undertaken by peroxyformic acid (by adding formic acid and hydrogen peroxide in situ generation in this latex), produces this epoxidised latex.
The emulsion of epoxidised renewable oils of the present invention can be mixed with epoxidized natural rubber latex and condense, obtain the epoxy natural rubber that a kind of functionalized renewable oils is filled.
In order to have the better workability with silicon-dioxide, obtain polymkeric substance of the present invention, it remains the primary formation of GMA monomer, that is, do not allow opening of this oxirane ring.This oxirane ring is kept not change or stable advantage is and is wherein formed compared with those of hydroxyl by open loop step in polymer chain, the workability of the improvement of the polymkeric substance obtained by this path.Due to strong hydrogen bonding, the polymer backbone presenting hydroxyl has the very strong interaction with silicon-dioxide hydroxyl, gives those compounds by the workability of non-constant.Attendant advantages of the present invention is the following fact: it does not relate to the use of strong acid or highly basic (being generally used for opening in the step of oxirane ring).Therefore, the conventional equipment produced for ESBR is at present used can to produce of the present invention generated product.
In order to protect this oxirane ring, the functionizing method of polymeric chain of the present invention is undertaken by using a kind of buffer system, and this buffer system allows to control latex pH in the scope of 8.5 to 9.5.The example of buffer system is phthalic acid disodium hydrogen/sodium dihydrogen orthophosphate, acetic acid/sodium acetate, boric acid/sodium tetraborate, dibasic sodium phosphate/sodium hydroxide, monosodium phosphate/phosphoric acid, KH2PO4/sodium hydroxide, Di-Sodium Phosphate/phosphoric acid, monosodium phosphate/sodium hydroxide, boric acid/sodium hydroxide, hydrogen phthalate dipotassium/KH2PO4, KH2PO4/sodium hydroxide, sodium tetraborate/hydrochloric acid, sodium carbonate/bicarbonate, Di-Sodium Phosphate/phosphoric acid, potassiumphosphate/potassium hydroxide, sodium tetraborate/sodium hydroxide, sodium bicarbonate/sodium hydroxide, ortho-phosphoric acid hydrogen sodium/sodium hydroxide, Repone K/sodium hydroxide.
Preferably be made up of phosphoric acid salt and acetate for the protection of the buffer system of epoxide group in the present invention.There is phosphatic preferred buffer system and comprise monosodium phosphate/phosphoric acid, KH2PO4/sodium hydroxide, potassiumphosphate/potassium hydroxide, Di-Sodium Phosphate/phosphoric acid, monosodium phosphate/sodium hydroxide, preferably there is potassiumphosphate/potassium hydroxide.The preferred buffer system with acetate comprises acetic acid/sodium acetate, acetic acid/sodium hydroxide, acetic acid/potassium hydroxide, acetic acid/sodium phosphate, preferably has acetic acid and potassium hydroxide.
The existence being combined in the epoxide group in this polymeric chain can be determined by Fourier transform infrared (FTIR) technology.In order to carry out this analysis, use PERKINELMER device model SpectrumOne.This program is also made up of to remove the residual monomer be present in this sample with ethanol redeposition twice in tetrahydrofuran (THF) (tetrahydrofyran) rubber solution.Then, by this rubber at room temperature and carry out drying under vacuo.FTIR analysis is carried out by the rubber film be deposited on zinc selenate pond.Fig. 1,2 and 3 respectively illustrates the FTIR spectrum of the functionalized ESBR of preparation in the standard ESBR and example 4 prepared in GMA monomer, example 1.Fig. 3 shows the absorption band (indicating the existence of oxirane ring in this polymer backbone) in 847cm-1 and do not absorb (indicating hydroxyl not to be present in this polymer backbone) in 3100-3300cm-1 region, this means do not have oxirane ring to open generation.
Rubber for tire industry uses the oil of 37.5phr (numbers of every hundred parts of rubber) to fill usually, so as to promote processing and avoid by the friction between other compositions of rubber, weighting agent and this compound preparation cause overheated.
Be intended to the renewable source of the extending oil had for rubber industry, test general soybean oil at first, but the oil observed on the hardening compound prepared with the rubber of this oil filling is oozed out (being assessed by compressive set: the hardening compound bearing compression during 3 days at 75 DEG C).This oozing out is low interaction due to rubber-oil.
In order to overcome this technical problem, the present invention proposes use and there is polymerizable functionalities monomer (preferred GMA) and the functionalized ESBR filled with functionalized renewable oils (preferred epoxidised soybean oil), to improve the interaction between polymkeric substance and oil, avoid oozing out and improving rubber property.
The triglyceride level molecule that soybean oil and vegetables oil are normally represented by Generalized chemical structure 3:
Wherein R
1, R
2and R
3it is the group from fatty acid ester.According to table 1, the feature of dissimilar oil is the radicals R in its structure
1, R
2and R
3relative proportion:
table 1: some plant oil compositions:
The vegetable oil type that can use as the extending oil for ESBR of the present invention comprises: soybean oil, Oleum Gossypii semen, Semen Ricini oil, plam oil, linseed oil, Oleum Cocois, sunflower oil, pine-tree oil, Semen Maydis oil, sweet oil, peanut oil, rapeseed oil, Canola Oil, sesame oil, Rice pollard oil, Jatropha oil or its mixture, preferred soybean oil, Oleum Gossypii semen, Semen Ricini oil, plam oil and linseed oil, preferred soybean oil and Oleum Gossypii semen and more preferably soybean oil.
Catalyzer can be used to carry out the transesterify of soybean oil and ethanol.In this reaction, triglyceride level and alcohol react under the existence of a kind of strong acid or highly basic.The product obtained is the mixture (chemical reaction 1) of glycerine and fatty acid alkyl ester:
Wherein R ', R ", R " ' represent fatty acid group.
As indicated in above reaction, the triglyceride level of this process need 1mol and the alcohol of 3 moles.This complete procedure relates to three continuous and reversible reactions, and formation triglyceride and monoglyceride are as intermediate product.The composition of final product will depend on reaction conditions, as the type of temperature, stoichiometry (alcohol/triglyceride level mol ratio), catalyzer.In transesterification reaction and after removing glycerine, this composition is: fatty-acid ethyl ester, triglyceride, monoglyceride and triglyceride level.
Oil composition after the ester exchange can pass through thermogravimetric analysis (TGA), use from the TGA device model Q50 of TA instrument company (TAInstruments), the N from the temperature jumps of 50 DEG C to 600 DEG C (temperatureramp), 60ml/min
2the sample quality of flow, about 5.0000mg is determined.Fig. 4 shows the signal thermogram (mass loss and derivative reduced temperature) of the vegetables oil sample after transesterification reaction.
The composition of the soybean oil of the transesterify that can use as the extending oil for the ESBR in the present invention must comprise: fatty-acid ethyl ester, triglyceride and triglyceride level, by the fatty-acid ethyl ester from 5% to 60% change, triglyceride from 40% to 80% change and the triglyceride level composition from 0.01% to 99.9% change, preferably by the fatty-acid ethyl ester from 35% to 48% change, triglyceride from 50% to 75% change and the triglyceride level composition from 0.01% to 50% change, more preferably by the fatty-acid ethyl ester from 40% to 44% change, triglyceride from 56% to 60% change and the triglyceride level composition from 0.01% to 4% change.
After Exchange Ester Process, soybean oil also can be at least partially epoxidized.In the double bond of unsaturated compound, the epoxidation of the soybean oil of transesterify is there is in two steps.First, peracetic acid is prepared by the reaction of the acetic acid that represented by following chemical reaction 2 and hydrogen peroxide.
Second step is that the double bond of this unsaturated ester and peracetic acid react to produce epoxidised soybean oil.Following chemical reaction 3 is with the epoxidised illustrative example of ethyl linoleate.
The epoxidised amount of oil is easily realized by the mol ratio controlled between the oil and peracetic acid of transesterify by vegetable oil production person.The epoxidised degree of possible soybean oil is between 0.01% to 6.3%.For the extending oil in the ESBR be used as in the present invention, epoxidised degree is between 2.5% to 4.5% and preferably between 3.3% to 3.5%.
The renewable oils being used as the extending oil of functionalized ESBR of the present invention is filled in this functionalized styrene-butadiene copolymer with 25 to 42phr, the preferably amount of 37.5phr.
Functionalized ESBR multipolymer with the filling of functionalized renewable oils of the present invention presents the mooney viscosity (ML1+4,100 DEG C) of 35 to 65, preferably 40 to 60.
The functionalized ESBR using epoxidised soybean oil of the present invention to fill prepares using silicon-dioxide and/or carbon black as the compound for tire of weighting agent and is hardened.Have evaluated characteristic as rheometry, tension test, wearing and tearing, ooze out observation, wet grip and rolling resistance.
The rubber hardening compound with the functionalized rubber of filling with epoxidised renewable oils of the present invention can be industrially used to prepare general technology article, these technology articles comprise tire, tyre surface, conveying belt, sole, pipeline, carpet-like coverture, flexible pipe and moulded product generally, consider that each producer has specific preparation according to its product specification and application.
Ooze out except problem except solving, compared with the general ESBR filled with extending oil, mainly in the compound preparation for tire and technology article present superior characteristic as rupture stress, tear strength, wear resistance, wet grip and rolling resistance using silicon-dioxide as the hardening compound of the use of reinforcing filler functionalized styrene-butadiene-methyl glycidyl acrylate of filling by epoxidised soybean oil of the present invention.
example
Following instance is presented and these examples are not intended to limit its scope in order to understand the present invention better.
Example 1
By the SBR latex of letex polymerization preparation standard
By the SBR latex of letex polymerization preparation standard in 20 liters of reactors.First, by emptying for this reactor and then use nitrogen pressurization, repeat this process twice, when this reactor under vacuo time complete.Carry out this program to avoid there is oxygen in media as well, the initiation of oxygen quenching polyreaction.Following composition is loaded: water (8 in reactor under this vacuum, 700g), there is a collection of emulsifying agent (2 of the sylvite of lipid acid and sylvic acid, 330g), 1,3-divinyl (3,830g), vinylbenzene (Isosorbide-5-Nitrae 86g), pinane hydroperoxide (2.5g), a collection of activator (390g) with water, ferrous sulfate, EDTA and sodium sulfoxylate formaldehyde, uncle-lauryl mercaptan (10g).At 7 DEG C, carry out batchwise polymerization and stop (time length of about 7 hours) with n-isopropylhydroxyla (n-isopropylhydroxylamine) (15g) when the transformation efficiency of 60%.By the standard latex of acquisition and the emulsion blending of a kind of extending oil (there is low-level polycyclc aromatic compound).These oil can be: TRAE (the residual aromatic series extract processed), HN (heavy cyclic hydrocarbon), TDAE (the overhead product aromatic series extract processed), MES (gentle Extraction solvent compound).The amount of oil in this dry rubber substance is 37.5phr (numbers of every hundred parts of rubber).In 20 liters of stainless steel vessels, with the steam heating at 65 DEG C, under mechanical stirring, use coagulant aids and sulfuric acid condensation latex and the emulsion of oil.By the chip demineralized water that formed in the process so as to remove in the medium remaining resistates as salt, soap etc.These chips are placed in stainless steel sift and at 65 DEG C, under forced air circulation, continue 18 hours to obtain this dry rubber substance.
Example 2
The oil filling copolymer of butadiene-styrene obtains in the mode identical with example 1, blended and obtain except this rubber except preparing general soybean oil emulsion so that with this latex.The amount of general soybean oil in this dry rubber substance is 37.5phr.
Example 3
The oil filling copolymer of butadiene-styrene obtains in the mode identical with example 1, blended and obtain except this rubber except preparing epoxidised soybean oil emulsion so that with this latex.The amount of epoxidised soybean oil in this dry rubber substance is 37.5phr.
Example 4
Functionalized SBR latex is prepared by letex polymerization
Functionalized SBR latex is prepared by adding functional monomer's glycidyl methacrylate (GMA) when being polymerized and starting.Because the amount of GMA in this reaction medium is little, thus separately a kind of blend of preparation GMA in vinylbenzene to promote its diffusion in the medium.By the reactor nitrogen pressurization of the 20L under a vacuum, repeat this process twice, when this reactor under vacuo time complete.Carry out this program to avoid there is oxygen in media as well, the initiation of oxygen quenching polyreaction.Following composition is loaded: water (8,500g), a collection of emulsifying agent (2,330g) with the sylvite of lipid acid and sylvic acid, a collection of buffer system (phosphoric acid 85%:2.1g in reactor under this vacuum; Acetic acid 99%:5.4g; Potassium hydroxide 50%:15.3g; Water: 200.0g; PH=8.7), 1,3-divinyl (3,830g), vinylbenzene (1,242g), the cinnamic blend of GMA/ (106/133g), pinane hydroperoxide (2.5g), a collection of activator (390g) with water, ferrous sulfate, EDTA and sodium sulfoxylate formaldehyde, uncle-lauryl mercaptan (10g).At 7 DEG C, carry out batchwise polymerization and stop (the polymerization time length of about 5 hours) with n-isopropylhydroxyla (15g) when the transformation efficiency of 60%.The pH of final latex is 9.2.By the functionalized latex of acquisition and the emulsion blending of a kind of extending oil (there is low-level polycyclc aromatic compound).These oil can be: TRAE (the residual aromatic series extract processed), HN (heavy cyclic hydrocarbon), TDAE (the overhead product aromatic series extract processed), MES (gentle Extraction solvent compound).The amount of oil in this dry rubber substance is 37.5phr (numbers of every hundred parts of rubber).In 20 liters of stainless steel vessels, with the steam heating at 65 DEG C, under mechanical stirring, use coagulant aids and sulfuric acid condensation latex and the emulsion of oil.By the chip demineralized water that formed in the process so as to remove in the medium remaining resistates as salt, soap etc.These chips are placed in stainless steel sift and at 65 DEG C, under forced air circulation, continue 18 hours to obtain this dry rubber substance.
Example 5
Oil-filled functionalized styrene-butadiene copolymer obtains in the mode identical with example 4, blended and obtain except this rubber except preparing general soybean oil emulsion so that with this latex.The amount of general soybean oil in this dry rubber substance is 37.5phr.
Example 6
Oil-filled functionalized styrene-butadiene copolymer obtains in the mode identical with example 4, blended and obtain except this rubber except preparing epoxidised soybean oil emulsion so that with this latex.The amount of epoxidised soybean oil in this dry rubber substance is 37.5phr.This example with functionalized soybean oil fill functionalized styrene-butadiene copolymer present following characteristic: the styrene content of combination: 21.0%wt; Polybutadiene microstructure: cis-1.4=9.5%wt; Anti-form-1 .4=76.3%wt; Vinyl 1.2=14.2%wt; Mooney viscosity (ML1+4,100 DEG C): 45.8; Molecular-weight average (Mw) by GPC (gel permeation chromatography): 356,000g/mol.
Prepared by compound
Following preparation is for having compound preparation (corresponding earth's surface 2 and 3) of carbon black and/or silicon-dioxide.
Table 2: composition prepared by the compound for having carbon black
| Component | *phr |
| Rubber | 96.2 |
| Buna CB 24 (polyhutadiene) | 30.0 |
| Carbon black (N-339) | 75.0 |
| Oil (cyclic hydrocarbon, general soybean or epoxidised soybean) | 11.3 |
| Stearic acid | 3.00 |
| Zinc oxide | 3.0 |
| Antioxidant N-1,3-dimethylbutyl-N'-Phenyl-p-phenylenediamine (6-PPD) | 2.0 |
| N, N'-vulkacit D (difenilguanidina) (DPG) | 0.3 |
| N tert butyl benzothiazole 2 sulfenamide | 1.3 |
| (N-tert-butyl-2-benzothiazoleslfenamide)(TBBS) | |
| Sulphur | 2.0 |
*the number of phr: every hundred parts of rubber
table 3:for composition prepared by the compound with silicon-dioxide
| Component | phr |
| Rubber | 96.2 |
| Buna CB 24 (polyhutadiene) | 30.0 |
| Silicon-dioxide (Zeozil 1165MP) | 70.0 |
| Zinc oxide | 3.0 |
| Sulphur | 1.6 |
| Stearic acid | 1.0 |
| Carbon black (N-339) | 5.0 |
| N tert butyl benzothiazole 2 sulfenamide (TBBS) | 1.0 |
| Oil (cyclic hydrocarbon, general soybean or epoxidised soybean) | 11.3 |
| Antioxidant N-1,3-dimethylbutyl-N'-Phenyl-p-phenylenediamine (6-PPD) | 2.0 |
| Silane (Si 69) | 5.6 |
| N, N'-vulkacit D (DPG) | 2.0 |
test
According to ASTMD1646, use unhardened rubber combination, to determine after 1min (ML1+1/100 DEG C) and the mooney viscosity of (ML1+4/100 DEG C) and the Mooney relaxation after 10 and 30 seconds after 4min:
MDR2000EMonsanto rheometer auxiliary under at 160 DEG C, in a rheometer, have studied the hardening characteristics of mixture according to DIN53529.In this way, characteristic data is determined as F
minimum, F
maximum, F
maximum-F
minimum, t
10, t
50, t
90and t
95, and also have F
15min, F
20min, F
25 minand F
25min-F
maximum.
According to DIN53529 the 3rd part, definition is:
F
minimum: at sclerosis instrument (vulcameter) reading at crosslinked isothermal minimum value place
F
maximum: at the sclerosis instrument reading at crosslinked isothermal maximum value place
F
maximum-F
minimum: the difference of sclerosis instrument reading between the minimum and maximum
T
10: the time obtaining the transformation efficiency of 10%
T
50: the time obtaining the transformation efficiency of 50%
T
90: the time obtaining the transformation efficiency of 90%
T
95: the time obtaining the transformation efficiency of 95%
Reversal characteristics is characterized by following parameter:
F
15min: the sclerosis instrument reading after 15min.
F
20min, the sclerosis instrument reading after 20min.
F
25min, the sclerosis instrument reading after 25min.
F
25min-F
maximumsclerosis instrument reading after 25min and the difference between maximum value
A kind of feature with the rubber combination of good reversal characteristics is the sclerosis instrument reading of substantially constant during long setting time; That is, should be in minimum relative to the change of this sclerosis instrument maximum value.Along with the reduction (" reverse ") on the increase sclerosis instrument reading of setting time is definitely undesirable.This is the instruction of the aging property of the difference of hardening product, wherein in use between period degree of crosslinking or modulus reduce.Undesirable is equally rising (" modulus of advancing (marchingmodulus) ") on sclerosis instrument reading after reaching the maximum.The tolerance of degeneration-resistant turn for rubber stock is the difference (F of the sclerosis instrument reading between 25min and maximum value
25min-F
maximum).When inventive mixture, this value is <-0.47dNm.
Sample needed for characterizing for hardening product is by producing mixture press quenching under the hydraulic pressure of 120 bar.Curing condition for generation of these samples is described for independent series of trials.
Use these hardening products, determine following characteristic according to the standard of specifying:
DIN53505: the Xiao A hardness at 23 DEG C and 70 DEG C
DIN53512: the elasticity (" R23 ") at 23 DEG C and 70 DEG C
DIN53504: the stress value (σ under the strain of 10%, 25%, 50%, 100%, 200% and 300%
10, σ
25, σ
50, σ
100, σ
200, and σ
300), tensile strength and elongation at break
DIN53516: wearing and tearing
And
Tan δ (60 DEG C): dissipation factor at 60 DEG C (E "/E ')
E ' gives the instruction of the earth-grasping force of winter tyre tread on ice and snow.E ' is lower, and earth-grasping force is better.
Tan δ (60 DEG C) is the tolerance of hysteresis loss in the rolling of tire.Tan δ (60 DEG C) is lower, and the rolling resistance of tire is lower.
Tensile strength test carries out according to ASTMD412 (standard method of test for rigidified rubber and thermoplastic elastomer-tension force) program on obtained hardening compound,
Stress relaxation, and pre-hardening characteristic (Mooney viscosity meter))
Wearing and tearing are assessed by DIN method
Second-order transition temperature (Tg) by dsc (DSC) commercial measurement, and
Hardness is measured by Shore A method.
In the compound of sclerosis, the value of the tan δ at 0 DEG C and 60 DEG C is measured by DMA (dynamic mechanical analysis) technology.
Wet grip and rolling resistance are the important characteristics of tire two of must exist.Wet grip means safe and rolling resistance means fuel economy.The value of the tan δ at 0 DEG C is relevant to wet grip and more high better, and the value of tan δ at 60 DEG C is relevant to rolling resistance and more low better.
There is the carbon black compound from the rubber in example 1,2 and 3
In micro-mixer, according to the formula in table 2, the rubber from example 1,2 and 3 is used for preparing the compound with carbon black.For there is the oil that uses in the formula of the compound of carbon black and to be used in rubber identical, such as, for the cyclic hydrocarbon oil of example 1, the general soybean oil for example 2 and the epoxidised soybean oil for example 3.
table 4: the result with the hardening product of carbon black using the rubber from example 1,2 and 3:
The result of the rubber Tg in table 4 shows compared with the standard rubbers with extending oil (example 1), the standard rubbers (example 3) with epoxidised soybean oil presents the reduction on Tg, and this effect is more remarkable when having standard rubbers (example 2) of general soybean oil.
Ooze out the key property that (oil moves on the surface of sclerosis) is rubber compound.Usually, observe when oil and the poor compatibility of rubber and ooze out.
Compressive set is usually used to inspection and oozes out because it be 75 DEG C, carry out under time length of pressure and 3 days.Under the condition that these are extreme, if the interaction of polymkeric substance-oil is not effective, then oozes out and will occur.
The hardening compound with carbon black that as expected after compressive set prepared by the standard rubbers of use-case 1 does not illustrate that oil oozes out, but the hardening compound with carbon black prepared by the rubber of use-case 2 (having the standard rubbers of general soybean oil) and example 3 (having the standard rubbers of epoxidised soybean oil) presents oil oozes out.
Result in table 4 shows and present poor performance from the modulus with the hardening compound of carbon black of example 2 and 3, rupture stress, hardness and wearing and tearing compared with example 1, although the mooney viscosity of untreated rubber is very similar.
The result of the tan δ at 0 DEG C and 60 DEG C in table 4 shows the wet grip of the hardening compound of example 3 and rolling resistance performance is similar to example 1.
There is the silicon dioxide compound from the rubber in example 1,2 and 3
In micro-mixer, according to the formula in table 3, the rubber from example 1,2 and 3 is used for preparing the compound with silicon-dioxide.For there is the oil that uses in the formula of the compound of silicon-dioxide and to be used in rubber identical, such as, for the cyclic hydrocarbon oil of example 1, the general soybean oil for example 2 and the epoxidised soybean oil for example 3.Result illustrates in table 5.
table 5: the result with the hardening product of silicon-dioxide using the rubber from example 1,2 and 3:
The hardening compound with silicon-dioxide prepared by the standard rubbers (having general soybean oil) of the hardening compound with silicon-dioxide that after compressive set prepared by the standard rubbers of use-case 1 and use-case 2 and the standard rubbers (having epoxidised soybean oil) of example 3 does not illustrate that oil oozes out.
Compared with example 1 (there is the standard rubbers of extending oil), result from the modulus with the hardening compound of silicon-dioxide of example 2 (having the standard rubbers of general soybean oil) and example 3 (having the standard rubbers of epoxidised soybean oil), hardness and wearing and tearing presents poor performance, although the mooney viscosity of untreated rubber is similar.
Compared with example 1, the wet grip performance of the hardening compound of the example 2 and 3 shown in table 5 is poor.Compared with the rolling resistance performance of example 1, the performance of example 2 is slightly superior, and the performance of example 3 is similar.
There is the carbon black compound from the rubber in example 4,5 and 6
In micro-mixer, according to the formula in table 2, the rubber from example 4,5 and 6 is used for preparing the compound with carbon black.For there is the oil that uses in the formula of the compound of carbon black and to be used in rubber identical, such as, for the cyclic hydrocarbon oil of example 4, the general soybean oil for example 5 and the epoxidised soybean oil for example 6.Result is shown in table 6.
table 6: the result with the hardening product of carbon black using the rubber from example 4,5 and 6:
In table 6, the result of rubber Tg shows compared with the functionalized rubber (-55.0 DEG C) with extending oil of example 4, for functionalized rubber (-74.8 DEG C) reduction on Tg with general soybean oil of example 5.But this reduction is not so remarkable for the functionalized rubber (-65.9 DEG C) with epoxidised soybean oil of example 6.
The hardening compound with carbon black that after compressive set prepared by the rubber (having the functionalized rubber of extending oil) of use-case 4 and the hardening compound with carbon black prepared by the rubber of use-case 5 (having the functionalized rubber of general soybean oil) and example 6 (having the functionalized rubber of general soybean oil) do not illustrate that oil oozes out.
Compared with example 4 (there is the functionalized rubber of extending oil), the result of the modulus and rupture stress with the hardening compound of silicon-dioxide of the example 5 (having the functionalized rubber of general soybean oil) shown in table 6 and example 6 (having the functionalized rubber of epoxidised soybean oil) is poor, because the mooney viscosity of untreated rubber is also poor.Hardness result and the example 4 of example 5 and 6 are very similar.Wear results shows the remarkable improvement compared with example 4 on the hardening compound of example 5 and 6.
The wet grip performance that the result of the tan δ at 0 DEG C in table 6 shows the carbon black hardening compound of example 6 compared with example 5 is better and similar compared with example 4.At example 4, between 5 and 6, rolling resistance performance (the tan δ at 60 DEG C) is similar.
There is the silicon dioxide compound from the rubber in example 4,5 and 6
In micro-mixer, according to the formula in table 3, the rubber from example 4,5 and 6 is used for preparing the compound with silicon-dioxide.For there is the oil that uses in the formula of the compound of silicon-dioxide and to be used in rubber identical, such as, for the cyclic hydrocarbon oil of example 4, the general soybean oil for example 5 and the epoxidised soybean oil for example 6.Result illustrates in table 7.
table 7: the result with the hardening product of silicon-dioxide using the rubber from example 4 and 5:
The hardening compound with silicon-dioxide that after compressive set prepared by the rubber (having the functionalized rubber of extending oil) of use-case 4 and the hardening compound with silicon-dioxide prepared by the rubber of use-case 5 (having the functionalized rubber of general soybean oil) and 6 (having the functionalized rubber of epoxidised soybean oil) do not illustrate and ooze out.
The modulus (accordingly 93.2 and 96.2) that result in table 7 shows the silicon-dioxide hardening compound of example 5 and 6 compared with example 4 (126.7) is poor, because the mooney viscosity of untreated rubber is also poor, if but be in identical level compared with the silicon-dioxide hardening compound (92.0) with the standard rubbers of extending oil of the example 1 shown in table 5, although the Mooney (example 1 of table 5) of untreated rubber is higher in this case.If to compare with 5 with example 4 and compared with the silicon-dioxide hardening compound of the example 1 (having the standard rubbers of extending oil) in table 5, rupture stress and the tear strength of the silicon-dioxide hardening compound of example 6 present better properties.
Other key properties of tire composition are wearing and tearing, the tan δ at 0 DEG C and the tan δ at 60 DEG C, and they mean wear resistance (weather resistance), wet grip (security) and rolling resistance (fuel economy) accordingly.If with example 4 with 5 silicon-dioxide hardening compound to compare and compared with the silicon-dioxide hardening compound of the example 1 (having the standard rubbers of extending oil) in table 5, the result of these the 3 kinds of characteristics in the table 7 of the silicon-dioxide hardening compound of example 6 (having the functionalized rubber of epoxidised soybean oil) presents better properties.
Improvement in the characteristic mentioned of the silicon-dioxide hardening compound of example 6 is the good interactional instruction of polymkeric substance-oil, and when functionaliseding both them, it is the functionalized rubber product that functionalized renewable oils of the present invention is filled.
Claims (16)
1. an oil-filled functionalized styrene-butadiene copolymer, wherein this functionalized styrene-butadiene copolymer comprise the styrene-based of 15 to the 50wt.% of this multipolymer based on 100wt.% repeating unit, based on the repeating unit based on divinyl of 42 to the 80wt.% of this multipolymer of 100wt.% and 5 to the 43wt.% of this multipolymer based on 100wt.% the unit based at least one functional monomer and wherein this at least one extending oil be based on vegetables oil.
2. oil-filled functionalized styrene-butadiene copolymer according to claim 1, wherein this functional monomer and this styrene monomer and butadiene monomers are to form this functionalized multipolymer, and therefore this functionalized multipolymer represents a kind of functionalized trimer.
3. oil-filled functionalized styrene-butadiene copolymer according to claim 2, comprises 0.3 to the 10wt.% of this multipolymer based on 100wt.%, preferably 0.5 to 5.0wt.% and the unit based on this functional monomer of more preferably 0.7 to 3.5wt.%.
4. oil-filled functionalized styrene-butadiene copolymer according to claim 3, wherein this functionalized multipolymer has the mooney viscosity (ML1+4 at 100 DEG C) of 35 to 65, preferably 40 to 60, and passes through the molecular-weight average (Mw) of 100.000 to 2.200.000g/mol, preferably 200.000 to 900.000g/mol that GPC (gel permeation chromatography) determines.
5. oil-filled functionalized styrene-butadiene copolymer according to claim 1, is wherein grafted to this functional monomer on this multipolymer.
6. oil-filled functionalized styrene-butadiene copolymer according to any one of claim 1 to 5, wherein this functional monomer is selected from lower group, this group is made up of the following: acrylate base monomer preferable methyl glycidyl acrylate, glycidyl acrylate, methacrylate hydroxypropyl acrylate, hydroxyethyl methylacrylate, vinyl cyanide, methacryloxypropyl trimethoxy silane, methacryloxypropyl three isopropoxy silane, or methacryloxypropyl silane.
7. oil-filled functionalized styrene-butadiene copolymer according to any one of claim 1 to 6, wherein this extending oil is selected from lower group, and this group is made up of the following: soybean oil, Oleum Gossypii semen, Semen Ricini oil, plam oil, linseed oil, Oleum Cocois, sunflower oil, pine-tree oil, Semen Maydis oil, sweet oil, peanut oil, rapeseed oil, Canola Oil, sesame oil, Rice pollard oil, Jatropha oil with and composition thereof.
8. oil-filled functionalized styrene-butadiene copolymer according to claim 7, wherein transesterify, preferably this extending oil of epoxidation.
9. the oil-filled functionalized styrene-butadiene copolymer according to claim 7 or 8, wherein uses this extending oil with 25 to 42phr, the preferably amount of 37.5phr.
10., for the production of a method for oil-filled functionalized styrene-butadiene copolymer according to any one of claim 1 to 9, the method comprises:
(1a) use a kind of buffer system and control pH Emulsion polymerized styrene in the scope of 8.5 to 9.5 of latex, divinyl and functional monomer, wherein this buffer system is selected from lower group, this group is made up of the following: phthalic acid disodium hydrogen/sodium dihydrogen orthophosphate, acetic acid/sodium acetate, boric acid/sodium tetraborate, dibasic sodium phosphate/sodium hydroxide, monosodium phosphate/phosphoric acid, KH2PO4/sodium hydroxide, Di-Sodium Phosphate/phosphoric acid, monosodium phosphate/sodium hydroxide, boric acid/sodium hydroxide, hydrogen phthalate dipotassium/KH2PO4, KH2PO4/sodium hydroxide, sodium tetraborate/hydrochloric acid, sodium carbonate/bicarbonate, Di-Sodium Phosphate/phosphoric acid, potassiumphosphate/potassium hydroxide, sodium tetraborate/sodium hydroxide, sodium bicarbonate/sodium hydroxide, ortho-phosphoric acid hydrogen sodium/sodium hydroxide, Repone K/sodium hydroxide, or
(1b) by a kind of styrene-butadiene copolymer of being obtained by Emulsion polymerized styrene and divinyl and functional monomer's grafting,
(1c) by carrying out directly this polymer chain functionalized via with this general ESBR of polymeric chain modification of the functionalized general ESBR of epoxide group, and
(2) this analog copolymer that will be obtained by (1a), (1b) or (1c) and at least one based on vegetables oil extending oil, preferably epoxidized vegetable oil is blended.
11. methods according to claim 10, wherein this functional monomer is selected from lower group, this group is made up of the following: acrylate base monomer is as glycidyl methacrylate, glycidyl acrylate and analogue, methacrylate hydroxypropyl acrylate, hydroxyethyl methylacrylate and analogue, vinyl cyanide, methacryloxypropyl trimethoxy silane, methacryloxypropyl three isopropoxy silane, methacryloxypropyl silane and analogue.
12. according to claim 10 or method according to claim 11, wherein this extending oil is selected from lower group, and this group is made up of the following: soybean oil, Oleum Gossypii semen, Semen Ricini oil, plam oil, linseed oil, Oleum Cocois, sunflower oil, pine-tree oil, Semen Maydis oil, sweet oil, peanut oil, rapeseed oil, Canola Oil, sesame oil, Rice pollard oil, Jatropha oil or its mixture.
13. methods according to claim 12, wherein this extending oil of transesterify makes it have mixture based on 100wt.% from the fatty-acid ethyl ester of 5 to 60wt.%, the mixture of the triglyceride from 40 to 80wt.% and the triglyceride level from 0.01 to 99.9wt.%, preferably produce by the fatty-acid ethyl ester from 35% to 48% change, the composition of the triglyceride from 50% to 75% change and the triglyceride level composition from 0.01% to 50% change, and more preferably produce by the fatty-acid ethyl ester from 40% to 44% change, the composition of the triglyceride from 56% to 60% change and the triglyceride level composition from 0.01% to 4% change.
14. methods according to claim 13, the extending oil of wherein this transesterify of epoxidation make it have 2.5% to 4.5% and preferably 3.3% to 3.5% epoxidation level.
15. 1 kinds of rubber combinations, this rubber combination comprises oil-filled functionalized styrene-butadiene copolymer according to any one of claim 1 to 9 and at least one carbon black and/or at least one silicon-dioxide.
16. rubber combinations according to claim 15 for the production of technology article, the purposes of preferred tire, tyre surface, conveying belt, sole, pipeline, carpet-like coverture, flexible pipe and moulded product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20130164219 EP2792689A1 (en) | 2013-04-18 | 2013-04-18 | Oil extended functionalized styrene-butadiene copolymer |
| EP13164219.1 | 2013-04-18 | ||
| PCT/EP2014/057693 WO2014170356A1 (en) | 2013-04-18 | 2014-04-16 | Oil extended functionalized styrene-butadiene copolymer |
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Also Published As
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| SG11201508408PA (en) | 2015-11-27 |
| BR112015026369A2 (en) | 2014-10-23 |
| MY179711A (en) | 2020-11-11 |
| RU2015149122A (en) | 2017-05-24 |
| HUE034887T2 (en) | 2018-03-28 |
| TW201509967A (en) | 2015-03-16 |
| BR112015026369B1 (en) | 2020-07-21 |
| JP6389240B2 (en) | 2018-09-12 |
| BR112015026369A8 (en) | 2018-02-06 |
| US9902837B2 (en) | 2018-02-27 |
| CN105121476B (en) | 2018-01-02 |
| US20160068659A1 (en) | 2016-03-10 |
| HK1221967A1 (en) | 2017-06-16 |
| WO2014170356A1 (en) | 2014-10-23 |
| EP2792689A1 (en) | 2014-10-22 |
| KR102253246B1 (en) | 2021-05-18 |
| EP2986647B1 (en) | 2017-07-26 |
| ZA201508478B (en) | 2016-10-26 |
| KR20160012135A (en) | 2016-02-02 |
| JP2016515661A (en) | 2016-05-30 |
| PL2986647T3 (en) | 2018-03-30 |
| MX2015014627A (en) | 2016-08-08 |
| SA515370007B1 (en) | 2017-07-24 |
| EP2986647A1 (en) | 2016-02-24 |
| RU2662517C2 (en) | 2018-07-26 |
| ES2640791T3 (en) | 2017-11-06 |
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